Cyclohexyl phenethylether derivative

ABSTRACT

Described is the genus of compounds defined according to the structure: ##STR1## wherein R 1 , R 2 , R 3  and R 4  are the same or different and each represents methyl or hydrogen with the proviso that one of R 2 , R 3  and R 4  is methyl and the other two of R 2 , R 3  and R 4  are hydrogen which have been found to be useful in augmenting or enhancing the aroma of perfumes and perfumed articles as well as colognes and, in addition, in combatting tobacco beetles of the species Lasioderma serricorne (F.). Also described are novel processes for preparing such cyclohexyl phenethylether derivatives by reacting cyclohexene having the structure: ##STR2## with a phenethyl alcohol derivative having the structure: ##STR3## in the presence of an acid catalyst.

This application is a continuation-in-part of application for UnitedStates Letters Patent, Ser. No. 192,238 filed on Sept. 30, 1980.

BACKGROUND OF THE INVENTION

This invention relates to phenethyl cyclohexylether derivatives, a novelprocess for preparing same, and to the use thereof in combatting insectsas a result of the discovery that such cyclohexyl phenethyletherderivatives are tobacco beetle pheromones or ectohormones; and inaddition to the use of such phenethyl cyclohexylether derivatives inaugmenting or enhancing the aroma of perfumes, colognes and perfurmedarticles (e.g., solid or liquid anionic, cationic, nonionic orzwitterionic detergents, fabric softeners, fabric softener articles,hair conditioners, odorants and deodorants). Obviously then, theinvention also relates to a pleasant smelling pheromone or ectohormoneuseful for combatting insects yet, at the same time, not repulsive tothe individual or group of individuals applying the pheromone orectohormone to the area where the insects are to be combatted.

Pheromones or ectohormones are secreted by insects as so called sociallyactive ingredients, e.g., as sexual attractant or aggregation substance.The use of these pheromones or ectohormones is known to attract insectsinto certain small sections of a contaminated area, to concentrate themin this area and then to destroy the insects in any known way, e.g.,mechanically, chemically or with insecticides. This method leads to avery economical and concentrated use of the actual insecticides,especially of insecticides which are ecologically dangerous, whereby thespraying of large parts of the contaminated area in any expensive way,e.g., by spraying insecticides with an aeroplane, is avoided.

No pheromones have been discovered up to the present time for use withLasioderma serricorne (F.). Thus, the pheromones known up to the presenttime belong to a large variety of chemical substances and are, as arule, effective only with respect to certain insects such as, forexample, for use in combatting insects of the order coleoptera and thefamily scolytidae and platypodidae which beetles cause substantialdamage to forests and to the wood of trees generally as taught in U.S.Pat. No. 3,927,207 issued on Dec. 16, 1975.

Another problem as yet unsolved by the prior art concerns theutilization, either in conjunction with or as pheromones or ectohormonesfor insect attractants, of fragrance imparting, augmenting or enhancingagents. Such fragrance imparting, augmenting or enhancing agents must beeither identical to or, at the very least, compatible with thepheromones or ectohormones. Previously such pheromones or ectohormoneshaving their own aroma profiles usually have an aroma profile whicheither was esthetically displeasing or, at the very best, incapable ofcovering or deodorizing the chemical-like sharp, abrasive aroma of theinsecticides used against the insects.

An optimal solution to the foregoing problems would be to create, in onechemical, a pheromone or ectohormone; an insecticide; and an aromaaugmenting or enhancing substance which is compatible with saidpheromone or ectohormone and with said insecticide.

Notwithstanding the aforementioned pheromone or ectohormone propertiesand notwithstanding the aforementioned insecticide properties, chemicalcompounds which can provide dry green hyacinth-like, rose-like, fruityand galbanum-like aromas which are both rich and full bodied as well aslong lasting are desirable in the art of perfumery. Many of the naturalmaterials which provide such fragrances and contribute such desirednuances to perfumery compositions are high in cost, unattainable attimes, vary in quality from one batch to another and/or are generallysubject to the usual variations of natural products.

There is, accordingly, a continuing effort to find synthetic materialswhich will replace, enhance or augment the fragrance notes provided bynatural essential oils or compositions thereof. Unfortunately, many ofthese synthetic materials either have the desired nuances only to arelatively small degree or else contribute undesirable or unwanted odorto the compositions. The search for materials which can provide morerefined, more natural-like, long-lasting dry green hyacinth, rose,fruity and galbanum aromas have been difficult and relatively costly inthe areas of both natural products and synthetic products.

Arctander in "Perfume and Flavor Chemicals (Aroma Chemicals)", VolumeII, 1969 describes phenylethyl alcohol as having a rose aroma.

Phenethyl propionate has been disclosed in the Journal of EconomicEntomology, 66, (5), 1973, and has been indicated by McGovern et al tobe an attractant for Popillia japonica Newman (Japanese beetles)particularly in combination with eugenol. Indeed, in that same paper byMcGovern et al, it is indicated that trans-2-hexenal, a well-knownperfume ingredient, is also a Japanese beetle attractant. The phenethylpropionate has the structure: ##STR4##

In another paper by McGovern et al, Journal of Economic Entomology,Volume 63, No. 1, page 276, it is indicated that methylcyclohexanepropionate and certain related chemicals are also attractantsfor Popillia japonica Newman.

Research concerning Lasioderma serricorne (F.) and attractants thereforare limited to the use of extracts of natural food odors. Thus, thepaper by Fletcher and Garrett entitled "Ovipositional Response of ThreeStrains of the Cigarette Beetle to Extracts of Food Odors" in TobaccoInternational, 182 (5), pages 166-169, Mar. 7, 1980, Fletcher andGarrett disclose that the ovipositional response of three strains of thecigarette beetle is a function of different food odor attractants.

Nothing in the prior art, however, discloses the unexpected, unobviousand advantageous properties of the phenethyl cyclohexylethers having thegeneric structure: ##STR5## wherein R₁, R₂, R₃ and R₄ are the same ordifferent and each represents methyl or hydrogen with the proviso thatone of R₂, R₃ and R₄ is methyl and the other two of R₂, R₃ and R₄ arehydrogen; or processes for preparing same by reacting the phenethylalcohol derivatives with cyclohexene. These compounds are not onlyuseful per se for augmenting or enhancing the aroma of perfumecompositions, colognes and perfumed articles but are also useful asLasioderma serricorne (F.) pheromones and, in addition, as Lasiodermaserricorne (F.) insecticides.

Ethers containing the phenylethyl moiety, however, are known inperfumery. Thus, Ishikawa et al, Japanese Kokai No. 77-07911 of Jan. 21,1977 (abstracted in Chem. Abstracts 87:135063q) discloses the genus ofcompounds defined according to the structure: ##STR6## as being usefulin perfumery; wherein R is alkyl; alkenyl; aryl; aralkyl; as well ascycloalkyl and R¹ is hydrogen or the same as R and R¹ is hydrogen or thesame as R and R² is alkyl or phenyl alkyl. Furthermore, U.S. Pat. No.3,734,970 discloses the use of the compound having the structure:##STR7## as being useful in augmenting or enhancing perfume aromas. Itis indicated that this compound is prepared by reacting phenylethylalcohol with an aluminum mercury couple to form the triphenyl ethoxyaluminum and the triphenyl ethoxy aluminum is then reacted withdimethoxy sulfoxide to produce the phenylethylmethylether. FrenchDemande No. 2,373,276 of July 7, 1978 (abstracted in Chem. Abstracts90:127414b(1979) discloses the compound having the structure: ##STR8##as being useful in augmenting or enhancing perfumes such as lilacperfumes.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is the GLC profile for the reaction product of Example IA at theend of the reaction and just prior to distillation.

FIG. 1B is the GLC profile for fraction 8 of the distillation product ofthe reaction product of Example IA which contains phenethylcyclohexylether having the structure: ##STR9##

FIG. 1C is the GLC profile for fraction 10 of the distillation productof the reaction product of Example IA containing the compound having thestructure: ##STR10##

FIG. 1D is the GLC profile for fraction 12 of the distillation productof the reaction product of Example IA containing the compound having thestructure: ##STR11##

FIG. 2 is the NMR spectrum for peak "A" of the GLC profile of FIG. IAwhich consists of the compound having the structure: ##STR12##

FIG. 3 is the NMR spectrum for peak "B" of the GLC profile of FIG. IAcontaining the compound having the structure: ##STR13##

FIG. 4 is the infra-red spectrum for peak "B" of the GLC profile of FIG.IA containing the compound having the structure: ##STR14##

FIG. 5 is the GLC profile for the reaction product of Example IBcontaining the compound having the structure: ##STR15## prior todistillation but subsequent to the sodium hydroxide wash of the reactionproduct.

FIG. 6A is the GLC profile for fraction 7 of the distillation product ofthe reaction product of Example IB containing the compound having thestructure: ##STR16##

FIG. 6B is the GLC profile for fraction 10 of the distillation productof the reaction product of Example IB containing the compound having thestructure: ##STR17##

FIG. 6C is the GLC profile for fraction 22 of the distillation productof the reaction product of Example IB containing the compound having thestructure: ##STR18##

FIG. 7A is the GLC profile of the crude reaction product prior todistillation of Example XVI containing the compound having thestructure: ##STR19##

FIG. 7B is the GLC profile for fraction 8 of the distillation product ofthe reaction product of Example XVI containing the compound having thestructure: ##STR20##

FIG. 8 is the NMR spectrum for fraction 6 of the distillation product ofthe reaction product of Example XVI containing the compound having thestructure: ##STR21##

FIG. 9 is the infra-red spectrum for fraction 6 of the distillationproduct of the reaction product of Example XVI containing the compoundhaving the structure: ##STR22##

FIG. 10A is the GLC profile for the crude reaction product prior todistillation of Example XVII containing the compound having thestructure: ##STR23##

FIG. 10B is the GLC profile for fraction 8 of the distillation productof the reaction product of Example XVII containing the compound havingthe structure: ##STR24##

FIG. 11 is the NMR spectrum for fraction 10 of the distillation productof the reaction product of Example XVII containing the compound havingthe structure: ##STR25##

FIG. 12 is the infra-red spectrum for fraction 10 of the distillationproduct of the reaction product of Example XVII containing the compoundhaving the structure: ##STR26##

DETAILED DESCRIPTION OF FIG. 5

FIG. 5 is the GLC profile for the reaction product of Example IBresulting from the reaction of cyclohexene and phenylethyl alcohol.

The peak designated by the numeral "1" is the peak indicating unreactedcyclohexene.

The peak designated by the numeral "2" in the GLC profile is the peakwhich represents phenylethyl alcohol.

The peak designated by the numeral "3" represents the peak for thereaction product of Example IB, cyclohexyl phenethylether.

The conditions for this GLC profile obtention are 220° C. isothermalusing a 1/8"×10'10% SE-30 column.

THE INVENTION

The present invention proposes the use of cyclohexyl phenethyletherderivatives defined according to the structure: ##STR27## wherein R₁,R₂, R₃ and R₄ are the same or different and each represents methyl orhydrogen with the proviso that one of R₂, R₃ and R₄ is methyl and theother two of R₂, R₃ and R₄ are hydrogen, for combatting beetles of theorder Lasioderma serricorne (F.) in such a manner that one or more ofsaid cyclohexyl phenethylether derivatives not only act as a pheromoneor ectohormone but also act as aroma augmenting or enhancing agents and,in addition, act as insecticides. Notwithstanding the pheromone andinsecticide properties of said cyclohexyl phenethylether derivatives,the instant invention also provides cyclohexyl phenethyletherderivatives as fragrances capable of augmenting or enhancing thefragrance of perfume compositions, colognes and perfumed articles (e.g.,solid or liquid anionic, cationic, nonionic or zwitterionic detergents,fabric softeners, dryer-added fabric softener articles, hairconditioners, deodorants and cosmetic powders). The present inventionalso proposes a new process for preparing said cyclohexyl phenethyletherderivatives according to the reaction: ##STR28## wherein R₁, R₂, R₃ andR₄ are the same or different and each represents methyl or hydrogen withthe proviso that one of R₂, R₃ and R₄ is methyl and the other two of R₂,R₃ and R₄ are hydrogen, which reaction is carried out under specificconditions as indicated, infra.

The cyclohexyl phenethylether derivatives of our invention are capableof augmenting or enhancing the dry green, hyacinth, rose, fruity andgalbanum aromas of perfumes, perfumed articles and colognes of ourinvention. Of course, as part of the perfumed articles of our invention,there are the "perfumed insecticide-pheromone" compositions of ourinvention.

The destruction of the Lasioderma serricorne (F.) insects can beachieved by distributing the cyclohexyl phenethylether or pheromonalattractants in the contaminated area at separate individual places,namely, by means of catch trees. These are impregnated with theattractants which may, if desired, act as insecticides too; or one ormore of the cyclohexyl phenethylether derivatives may be augmented byone or more additional insecticides whereupon the catch trees aresprayed with another insecticide either before or after the insects havegathered at the catch tree (whatever insects are still alive aftercontact with said cyclohexyl phenethylether derivatives). Instead ofusing one or more cyclohexyl phenethylether derivatives taken alone ortaken together with another insecticide, one may also use a chemicalsterilizing compound. Further, the catch tree may be treated with otherchemicals which can be burned. Another possible method for destroyinginsects with one or more of the cyclohexyl phenethylether derivatives ofour invention makes use of the disturbance or perturbance theory.Instead of physically destroying the insects with either highconcentrations of one or more of the cyclohexyl phenethyletherderivatives of our invention or by using one or more of the cyclohexylphenethylethers of our invention followed by additional insecticide, itis also possible to combine one or more of the cyclohexyl phenethyletherderivatives of our invention physically with one or more additionalstronger insecticides before using. Thus, it is possible now to spray acombination of one or more cyclohexyl phenethylethers which havepleasant aromas in combination with insecticides whose original aroma(s)are covered using one or more of the cyclohexyl phenethylether(s) incertain centrally located areas or in the form of rows in thecontaminated area. Furthermore, one or more of the cyclohexylphenethylethers can be mixed with the usual solid or liquid carriers orwith biocides such as stronger insecticides, pesticides or herbicides.The mixture may contain surface active agents to obtain a betterdistribution or adherence to the plants.

The cyclohexyl phenethylether derivatives of our invention may beprepared according to a conventional method by reacting cyclohexanolwith beta phenylethyl alcohol derivatives such as beta phenylethylalcohol in the presence of an acid such as sulfuric acid according tothe reaction: ##STR29## wherein R₁, R₂, R₃ and R₄ are the same ordifferent and each represents methyl or hydrogen with the proviso thatone of R₂, R₃ and R₄ is methyl and the other two of R₂, R₃ and R₄ arehydrogen. Thus, for example, the reaction: ##STR30## is typical of sucha reaction. Alternatively, an alkali metal phenethyl alcoholatederivative may be reacted with a cyclohexyl halide such as cyclohexylbromide or cyclohexyl chloride or an alkali metal cyclohexyl alcoholatemay be reacted with beta phenylethyl chloride or beta phenylethylbromide by means of a "Williamson" synthesis, conventional in theorganic chemistry art.

However, more efficiently and of lower cost is the carrying out of aprocess of reacting a beta phenylethyl alcohol derivative withcyclohexene in the presence of specific acid catalysts under specificconditions according to the reaction: ##STR31## wherein R₁, R₂, R₃ andR₄ are the same or different and each represents methyl or hydrogen withthe proviso that one of R₂, R₃ and R₄ is methyl and the other two of R₂,R₃ and R₄ are hydrogen.

The temperature of reaction may vary from 90° C. up to about 180° C. atfrom 1 atmosphere pressure up to 100 atmospheres pressure. Highertemperatures of reaction require higher pressures of reaction.

The mole ratio of phenylethyl alcohol derivative to cyclohexene may varyfrom 1:1 up to about 1:2.

Various acid catalysts can be used including mineral acids such assulfuric acid or methane sulfonic acid or paratoluene sulfonic acid; orthe acid catalyst may be a solid acid catalyst such as a sulfonatedcopolymer of styrene and divinyl benzene (e.g., "Amberlyst®15"manufactured by the Rohm & Haas Corporation of Philadelphia, Pa.) or anacid clay such as an activated clay adsorbent such as Filtrol®105 havingthe following properties:

    ______________________________________                                        Particle size analysis                                                        By Roller (10 liters/min. air rate)                                           0-5 Microns, Wt. %       8                                                    0-20 Microns, wt. %      43                                                   By Taylor Standard Sieve                                                      Through 100 Mesh, wt. %  100                                                  Through 200 Mesh, wt. %  95                                                   Through 325 Mesh, wt. %  78                                                   Apparent Bulk density, lb/cu. ft.                                                                      42                                                   Free moisture, wt. %     15                                                   Free and Combined moisture, wt. %                                                                      21                                                   (loss at 1700°  F.)                                                    Surface area (BET Method), Sq.M/gm.                                                                    300                                                  Acidity, phenolphthalein, mg.KOH/gm.                                                                   4.8                                                  Filter rate, cc/min.     38                                                   Oil retention, wt. %     35                                                   ______________________________________                                    

The weight ratio of acid catalyst to phenylethyl alcohol derivative mayvary from about 2 wt. % up to about 20 wt. %.

The time of reaction is primarily a function of four variables:

1. temperature of reaction

2. conversion desired

3. particular acid catalyst utilized and

4. concentration of acid catalyst in the reaction mass

In general, higher temperatures of reaction give rise to a shorterrequired time of reaction, but too high a temperature of reaction (e.g.,greater than about 180° C.) and/or too long a time of reaction causes adiminution of conversion due to product decomposition. In general,higher concentration of acid catalyst in the reaction mass gives rise toshorter time periods of reaction for a given conversion to the desiredcyclohexyl phenethylether derivative. Thus, in general, a time ofreaction may vary from about 1 hour up to about 48 hours.

Notwithstanding the pheromonal and insecticidal activity of thecyclohexyl phenethylether derivatives of our invention, the cyclohexylphenethylethers of our invention can be used to contribute long lastingdry green, hyacinth, rose, fruity and galbanum aromas which areunexpectedly full and rich for a very long period of time to perfumes,perfumed articles and colognes. As olfactory agents, the cyclohexylphenethylether derivatives of our invention can be formulated into orused as components as a "perfume composition" or can be used ascomponents of a "perfumed article" or the perfume composition may beadded to "perfumed articles".

Examples of the compounds prepared according to the process of ourinvention, the phenylethyl alcohol derivative reactant for producingsuch compound and the olfactory properties of such compound are setforth in Table I below:

                  TABLE I                                                         ______________________________________                                        Product Structure                                                                          Reactant     Olfactory Properties                                ______________________________________                                         ##STR32##                                                                                  ##STR33##   A long lasting dry green, hyacinth, rose and                                  galbanum aroma.                                      ##STR34##                                                                                  ##STR35##   A floral, green, galbanum-like aroma.                ##STR36##                                                                                  ##STR37##   An interesting low keyed burnt                      ______________________________________                                                                  fruity aroma.                                   

The term "perfume composition" is used herein to mean a mixture oforganic compounds including, for example, alcohols, aldehydes, ketones,nitriles, ethers in addition to and other than the cyclohexylphenethylether derivatives of our invention, lactones, natural essentialoils, synthetic essential oils and frequently hydrocarbons which areadmixed so that the combined odors of the individual components producea pleasant or desired fragrance. Such perfume compositions usuallycontain: (a) the main note or the "bouquet" or foundation stone of thecomposition; (b) modifiers which round off and accompany the main note;(c) fixatures which include odorous substances which lend a particularnote to the perfume throughout all stages of evaporation, and substanceswhich retard evaporation; and (d) top notes which are usuallylow-boiling, fresh-smelling materials.

In perfume compositions, the individual component will contribute itsparticular olfactory characteristics, but the overall effect of theperfume composition will be the sum of the effects of each of theingredients. Thus, the cyclohexyl phenethylether derivatives of ourinvention can be used individually or in combination to alter the aromacharacteristics of a perfume composition, for example, by highlightingor moderating the olfactory reaction contributed by another ingredientin the composition.

The amount of one or more of the cyclohexyl phenethylether derivativesof our invention which will be effective in perfume compositions dependsupon many factors including the other ingredients, their amounts and theeffects which are desired. It has been found that perfume compositionscontaining as little as 0.05% of one or a mixture of the cyclohexylphenethylether derivatives of our invention or even less can be used toimpart long lasting, interesting, very strong, dry green, hyacinth,rose, fruity and galbanum aromas to soaps, liquid and solid cationic,nonionic, anionic and zwitterionic detergents, cosmetic powders, liquidand solid fabric softeners, dryer-added fabric softener articles,optical brightener compositions and other products. The amount employedcan range up to 50% or more and will depend upon considerations of cost,nature of the end product and the effect desired on the finished productand particular fragrance sought.

One or more of the cyclohexyl phenethylether derivatives of ourinvention can be used alone or in combination with one another or in aperfume composition as an olfactory component in detergents and soaps,space odorants and deodorants; perfumes; colognes, toilet water; bathsalts; hair preparations such as lacquers, brilliantines, pomades andshampoos; cosmetic preparations such as creams, deodorants, hand lotionsand sun screens; powders such as talcs, dusting powders, face powder andthe like. When used as an olfactory component of a perfumed article, aslittle as 0.01% of one or a mixture of cyclohexyl phenethyletherderivatives will suffice to impart an interesting long lasting drygreen, hyacinth, rose, fruity and/or galbanum aroma. Generally no morethan 0.5% is required in the perfumed article.

In addition, the perfume composition can contain a vehicle or carrierfor the cyclohexyl phenethylether derivatives taken alone or taken incombination with other ingredients. The vehicle can be a liquid such asan alcohol such as ethanol, a glycol such as propylene glycol, or thelike. The carrier can be an absorbent solid such as a gum or componentsfor encapsulating the composition such as gelatin which can be used toform a capsule wall surrounding the perfume oil by means ofcoacervation.

It will thus be apparent that one or more of the cyclohexylphenethylether derivatives of our invention can be utilized to alter,modify, augment or enhance the aroma of a wide variety of consumablematerials including fragrance formulations, colognes, pheromones,insecticides and perfumed articles in general.

The following examples serve to illustrate our invention and thisinvention is to be considered restricted thereto only as indicated inthe appended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE IA PREPARATION OF CYCLOHEXYL PHENETHYLETHER

Reaction: ##STR38##

Into a 2 liter reaction vessel equipped with stirrer, thermometer,heating mantle and overhead condenser with azeotrope takeoff apparatusis placed 488 grams of betaphenylethyl alcohol; 440 grams ofcyclohexanol and 100 grams of concentrated sulfuric acid. The reactionmass is then heated to a temperature of 115° C. and maintained at atemperature in the range of 104°-127° C. at reflux while azeotropicallyremoving 80 ml water, for a period of 3 hours. At the end of the 3 hourperiod, a sample is analyzed by means of GLC analysis (conditions: 180°C. isothermal using an SE-30 packed column). FIG. 1A is the GLC profileof the reaction product at this point.

The resulting reaction mass is then distilled on a 1'×29/42 distillationcolumn yielding the following fractions:

    ______________________________________                                                  Vapor    Liquid   Vacuum  Reflux                                    Fraction  Temp.    Temp.    mm. Hg  Ratio                                     Number    °C.                                                                             °C.                                                                             pressure                                                                              R/D                                       ______________________________________                                        1         27        40      1.2     1/4                                       2         70       100      1.0     4/1                                       3         67       100      1.0     4/1                                       4         67       100              4/1                                       5         70       105      0.7     4/1                                       6                                   4/1                                       7         70       130      0.7     4/1                                       8         88       140              4/1                                       9         100      132      0.55    4/1                                       10        100      160              4/1                                       11        100      165              4/1                                       12        102      185      0.4     4/1                                       13        107      205      0.5     4/1                                       ______________________________________                                    

FIG. 1B is the GLC profile for fraction 8 of the distillation product ofthe reaction product of this example which contains phenethylcyclohexylether having the structure: ##STR39##

FIG. 1C is the GLC profile for fraction 10 of the distillation productof the reaction product of this example containing the compound havingthe structure: ##STR40##

FIG. 1D is the GLC profile for fraction 12 of the distillation productof the reaction product of this example containing the compound havingthe structure: ##STR41##

FIG. 2 is the NMR spectrum for peak "A" of the GLC profile of FIG. 1Awhich consists of the compound having the structure: ##STR42##

FIG. 3 is the NMR spectrum for peak "B" of the GLC profile of FIG. 1Acontaining the compound having the structure: ##STR43##

FIG. 4 is the infra-red spectrum for peak "B" of the GLC profile of FIG.1A containing the compound having the structure: ##STR44##

EXAMPLE IB

Reaction: ##STR45##

Phenethyl alcohol (1487 grams; 12.2 moles) and Amberlyst 15® catalyst (asulfonated phenyl polyethylene ion exchange resin manufactured by theRohm & Haas Corporation of Philadelphia, Pa. (85.4 grams)) are heated to110° C. 1000 grams (12.2 moles) of cyclohexene is added dropwise to thereaction mass over a period of 4.5 hours while maintaining the reactionmass at 110° C. During the addition of the cyclohexene, residual water(22 ml) is removed by azeotropic distillation through a water separatingtrap. The reaction mass is stirred at 110° C. for an additional 5.25hours. At this point in time, the reaction mass is cooled and thecatalyst is removed by filtration. The organic solution is washed with400 grams of 30% sodium hydroxide and then distilled through a 11/2"×12"Goodloe column yielding the following fractions:

    ______________________________________                                               Vapor    Liquid   Head Vac.      Weight                                Fraction                                                                             Temp.    Temp.    mm/Hg.  Reflux of                                    Number (°C.)                                                                           (°C.)                                                                           Pressure                                                                              Ratio  Fraction                              ______________________________________                                        1      35/30     75/130  300     100    236.7                                 2      25/74    121/105  3       9:1    77g                                   3       71       96      5.8     9:1     35.4                                 4       72      121      3.0     9:1    120.9                                 5       74      137      3.0     9:1    225.9                                 6      105      140      3.0     9:1     61.9                                 7      105      140      3.0     9:1     44.1                                 8      105      140      3.0     9:1     34.2                                 9      105      140      3.0     9:1    113g                                  10     105      142      2.6     1:1    82g                                   11     105      145      2.6     1:1    101.7                                 12     105      145      2.6     1:1    83g                                   13     105      139      2.6     1:1     92.7                                 14     105      140      2.6     1:1    116.3                                 15     105      140      2.6     1:1     84.7                                 16     105      137      2.6     1:1    100.8                                 17     105      138      2.6     1:1    107.3                                 18     105      140      2.6     1:1     90.8                                 19     105      142      2.6     1:1    97g                                   20     108      146      3mm     9:1    820g                                  21     108      157      3       9:1    111.5                                 22     108      163      3       9:1    79g                                   23     117      199      3       9:1     54.4                                 24     129      250      3       9:1    95.1g                                 ______________________________________                                    

Fractions 11-22 contain phenylethyl cyclohexyl ether having a purity ofgreater than 99%.

FIG. 5 is the GLC profile for the reaction product immediately after thesodium hydroxide wash and prior to distillation.

FIG. 6A is the GLC profile for fraction 7 of the distillation product ofthe reaction product of Example IB containing the compound having thestructure: ##STR46##

FIG. 6B is the GLC profile for fraction 10 of the distillation productof the reaction product of Example IB containing the compound having thestructure: ##STR47##

FIG. 6C is the GLC profile for fraction 22 of the distillation productof the reaction product of Example IB containing the compound having thestructure: ##STR48##

EXAMPLE II

Field tests are made each time using 100 male and 100 female Lasiodermaserricorne (F.) cigarette beetles. The beetles were released at acertain distance from the source of attraction which was treated withcyclohexyl phenethylether prepared according to either of Example IA orIB. Further, felled trees having already been contaminated with therespective beetles are positioned at both sides of the starting point.After a certain period of time the amount of insects gathered at thesource of attraction was determined thus indicating the effectiveness ofthe pheromonal mixture according to the invention.

Field tests with Lasioderma serricorne (F.) are made whereby thedistance between the starting point and the source of attraction is 50meters. Four independent field tests were made whereby 42% of the malebeetles and 46% of the female beetles gathered at each catch tree. Theconcentration of insects at the catch tree was 55% of the male insectsand 58% of the female insects. In all these tests the catch tree wasimpregnated with a 0.7% ethanolic solution of cyclohexyl phenethylether(7 gm cyclohexyl phenethylether per 92 gm of 95% aqueous ethanol).

EXAMPLE III

During two consecutive days several felled oak trees surrounding a fieldof tobacco plants were treated with 250 mg of phenethyl cyclohexyletherin 1.0% ethanolic solution. These trees were exposed in an area whichwere contaminated with Lasioderma serricorne (F.). After 3 to 4 days 100beetles per square meter were observed on the logs. Other untreated logsor trees in the direct neighborhood of the treated logs or trees showedvery few (about 12) insects per square meter on the average while othertrees at a distance of 10 to 20 meters showed no contamination.

EXAMPLE IV

In a large test field, mixtures of cyclohexyl phenethylether inadmixture with different DDT preparations, fluorine-containing mixturesand arsenic-containing mixtures as well as hexachloro-cyclohexane wereused. These mixtures contained also small amounts of surface-activeagents and carriers. The mixtures were applied to catch trees namelylogs of oak trees in an area of tobacco plants contaminated withLasioderma serricorne (F.). The distance between the catch trees wasalways 200 meters. After 8 days there was no contamination either in thetobacco fields or around the oak trees. About 92% of the Lasiodermaserricorne (F.) insects were destroyed. Surprisingly, it was found thatafter the fourth day the attracting effect was not diminished in spiteof dead insects being present. Furthermore, in those areas wherecyclohexyl phenethylether was used alone, the average number of insectsdestroyed was about 80% which in itself is surprising. Thus, thecyclohexyl phenethylether not only acts as a pheromone but also as aninsecticide. Furthermore, the entire area wherein the cyclohexylphenethylether was used had a faint pleasant floral aroma covering anyadverse and esthetically displeasing aroma of any other insecticidesthat were used.

EXAMPLE V

The following mixture is prepared:

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                        Phenylacetic acid    70.0                                                     Coumarin             20.0                                                     Phenylethylphenyl acetate                                                                          100.0                                                    Phenyl ethyl alcohol 5.0                                                      Benzyl benzoate      100.0                                                    Dimethylphenylethyl carbinol                                                                       10.0                                                     Methyl anthranilate  5.0                                                      Beta ionone          10.0                                                     Cyclohexyl phenethylether                                                                          30.0                                                     ______________________________________                                    

The cyclohexyl phenethylether prepared according to either of Example IAor IB imparts the dry green hyacinth, rose, galbanum-like aroma to thishoney fragrance while giving it a very warm undertone and imparting avery long lasting floral top note to this fragrance.

EXAMPLE VI PREPARATION OF A COSMETIC POWDER COMPOSITION

A cosmetic powder is prepared by mixing in a ball mill 100 grams oftalcum powder with 0.25 grams of the perfume composition preparedaccording to Example V. It has an excellent floral aroma.

EXAMPLE VII PERFUMED LIQUID DETERGENT

Concentrated liquid detergents (Lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818 issued onApr. 6, 1976) with floral aroma nuances and rose, galbanum andhyacinth-like top notes are prepared containing 0.10%, 0.15% and 0.20%of the fragrance prepared according to Example V. They are prepared byadding and homogeneously mixing the appropriate quantity of fragranceformulation prepared according to Example V in the liquid detergent. Thedetergents all possess excellent floral aromas with dry green hyacinth,rose and galbanum nuances, the intensity increasing with greaterconcentrations of perfume composition prepared according to Example V.

EXAMPLE VIII PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

The composition prepared according to Example V is incorporated into acologne at concentrations of 2.0%, 2.5%, 3.0%, 4.0%, 4.5% and 5.0% in80%, 85%, 90% and 95% aqueous food grade ethanol; and into handkerchiefperfumes at concentrations of 15%, 20% and 30% (in 80%, 85% and 95%aqueous food grade ethanol). A distinctive and definitive dry greenhyacinth, rose, galbanum, rich and full-bodied floral aroma is impartedto the cologne and to the handkerchief perfume at all levels indicated.

EXAMPLE IX PREPARATION OF SOAP COMPOSITION

100 grams of soap chips are mixed with 1 gram of the formulation ofExample V until a homogeneous composition is obtained. The homogeneouscomposition is heated under three atmospheres pressure at 180° C. for aperiod of three hours and the resulting liquid is placed into soapmolds. The resulting soap cakes, on cooling, manifest excellent floralaromas with dry green hyacinth, rose and galbanum nuances that are verylong lasting.

EXAMPLE X PREPARATION OF A SOLID DETERGENT COMPOSITION

A detergent is prepared from the following ingredients according toExample I of Canadian Pat. No. 1,007,948:

    ______________________________________                                                          Percent by Weight                                           ______________________________________                                        "Neodol 45-11" (a C.sub.14 -C.sub.15                                          alcohol ethoxylated with                                                      11 moles of ethylene oxide)                                                                       12                                                        Sodium carbonate    55                                                        Sodium citrate      20                                                        Sodium sulfate, water brighteners                                                                 q.s.                                                      ______________________________________                                    

This detergent is a "phosphate free" detergent. A total of 100 grams ofthis detergent is admixed with 0.15 grams of the honey based perfume ofExample V. Each of the detergent samples have an excellent floralhoney-like, dry green hyacinth, rose and galbanum aroma.

EXAMPLE XI DRYER-ADDED FABRIC SOFTENER ARTICLE

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396, a nonwoven cloth substrate useful as a dryer-addedfabric-softening article of manufacture is prepared wherein thesubstrate, the substrate coating and the outer coating and the perfumingmaterial are as follows:

1. a water "dissolvable" paper ("Dissolvo Paper");

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. an outer coating having the following formulation (m.p. about 150°F.):

57% C₂₀₋₂₂ HAPS

22% isopropyl alcohol

20% antistatic agent

1% of cyclohexyl phenethylether produced according to either of ExampleIA or IB

A fabric softening composition prepared as set forth above having a drygreen hyacinth, rose, galbanum and generally floral aroma characteristicconsists of a substrate having a weight of about 3 grams per 100 squareinches, a substrate coating of about 1.85 grams per 100 square inches ofsubstrate and an outer coating of about 1.4 grams per 100 square inchesof substrate, thereby providing a total aromatized substrate and outercoating weight ratio of about 1:1 by weight of the substrate. A pleasantfloral aroma is imparted in a pleasant manner to the head space in thedryer on operation thereof using the said dryer-added fabric softeningnonwoven fabric.

EXAMPLE XII

A liquid detergent composition prepared according to Example IV ofUnited Kingdom Pat. No. 1,498,520 whereby the following ingredients areadmixed:

    ______________________________________                                        Ingredient              Weight %                                              ______________________________________                                        Coconut alcohol ethoxylate                                                                            30%                                                   Linear alkyl benzene sulfonate,                                               triethanolamine salt (alkyl = C.sub.11.8 avg.)                                                        10%                                                   Potassium chloride      3%                                                    Triethanolamine         3%                                                    Triethanolammonium citrate                                                                            2%                                                    Ethyl alcohol           5%                                                    Soil release ether "D"  1.0%                                                  Cyclohexyl phenethylether prepared                                            according to either of Example IA or IB                                                               3.0%                                                  Water                   Balance                                               ______________________________________                                    

The soil release ether "D" is defined according to Table II on page 15of United Kingdom Pat. No. 1,498,520.

This composition is prepared by admixing all of the ingredientsexclusive of soil release ether "D" and agitating the mixture until allelectrolytes are dissolved. Soil release ether "D" is then admixed withthe solution in the form of a dry powder which passes through a 150 meshstandard sieve. The resulting composition is in the liquid state and iseasily pourable. The composition is found not to redden on contact withplastic bottles, does not gel when diluted with water and has along-lasting aroma which can be described as dry green hyacinth, rose,galbanum and rich and rather long lasting. Indeed, the aroma lasts forseveral weeks when exposed to the atmosphere.

This composition is added to an aqueous laundrying bath at aconcentration of 0.20% (weight) at a temperature of 55° C., waterhardness 7 grains per gallon and a pH of 10.0. Polyester and mixedpolyester/cotton fabrics are laundered in the bath for a period of 10minutes after which the fabrics are thoroughly rinsed with fresh waterand dried at ambient temperatures. The fabrics are provided with a soilrelease finish. The head space above the fabrics has a pleasant faintaroma which can be described as hyacinth, rose, and galbanum and alsorather long-lasting (about 3 days).

EXAMPLE XIII PREPARATION OF A COSMETIC POWDER COMPOSITION

A cosmetic powder is prepared by admixing in a ball mill, 100 grams oftalcum powder with 0.25 grams of phenethyl cyclohexylether preparedaccording to either of Example IA or IB. The resulting cosmetic powderhas an excellent dry green hyacinth, rose, galbanum, rich andfull-bodied floral fragrance which is very long-lasting.

EXAMPLE XIV PERFUMED LIQUID DETERGENT

Concentrated liquid detergents (Lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818 issued onApr. 6, 1976) with dry green hyacinth, rose, galbanum rich andfull-bodied floral aroma are prepared containing 0.10%, 0.15%, 0.20% and0.25% of cyclohexyl phenethylether prepared according to either ofExample IA or IB. They are prepared by adding and homogeneously admixingthe appropriate quantity of phenethyl cyclohexylether in the liquiddetergent. The detergents all possess intense long-lasting dry greenhyacinth, rose, galbanum and generally floral aroma characteristics.

EXAMPLE XV PREPARATION OF COLOGNES AND HANDKERCHIEF PERFUMES

Cyclohexyl phenethylether prepared according to either of Example IA orIB is incorporated into colognes at concentrations of 2.0%, 2.5%, 3.0%,3.5%, 4.0% and 4.5% in 80%, 85%, 90% and 95% aqueous food grade ethanol;and into handkerchief perfumes at concentrations of 15%, 20%, 25% and30% (in 80%, 90% and 95% aqueous ethanol). Distinctive dry greenhyacinth, rose, galbanum, rich and full-bodied floral aroma nuanceswhich are very long-lasting on dry-out (54 hours) are imparted to thecolognes and to the handkerchief perfumes at the various above levelsindicated.

EXAMPLE XVI PREPARATION OF CYCLOHEXYL HYDROTROPYL ETHER

Reaction: ##STR49##

Into a stirred slurry of 408 grams of betamethylphenylethyl alcohol and25 grams of Amberlyst® 15 (a polysulfonated polystyrene cation exchangeresin manufactured by the Rohm & Haas Company of Philadelphia, Pa.)maintained at 110° C. is added 246 grams of cyclohexene over a 2.75 hourperiod. The reaction mass is aged at 110° C. for an additional two hourswhereupon it is cooled and filtered. The solution is then heated atreflux with 80 grams of 30% aqueous sodium hydroxide. The reaction massis then cooled and washed with one liter of water. The organic layer isthen separated from the aqueous layer and distilled and fractions richin product are then fractionated through a 12"×1" Goodloe packed columnto yield the following fractions:

    ______________________________________                                               Vapor    Liquid                  Weight                                Fraction                                                                             Temp.    Temp.    mm/Hg.  Reflux of                                    Number (°C.)                                                                           (°C.)                                                                           Pressure                                                                              Ratio  Fraction                              ______________________________________                                        1      47/92    110/RO   1.4     9:1                                          2      85       125      1.4     9:1    17g                                   3      85       124      1.4     9:1    18g                                   4      85       124      1.4     3:1    24.5                                  5      97       119      1.4     2:1    31.5                                  6      87       125      1.4     2:1    31.6                                  7      93       127      1.4     2:1    27.5                                  8      86       129      1.2     2:1    21.6                                  9      86       136      1.2     2:1    22                                    10     94       145      1.2     2:1    11.3                                  11     102      146      1.2     2:1    13.6                                  12     108      160      1.2     2:1    17.1                                  13     105      185      1.2     2:1    3.6g                                  ______________________________________                                    

FIG. 7A is the GLC profile of the crude reaction product (conditions:1/8"×10' 10% SE 30 packed column operated at 180° C. isothermal).

FIG. 7B is the GLC profile for fraction 8 of the distillation product(conditions: 1/8"×10' 10% SE 30 packed column; programmed at 220° C.isothermal).

FIG. 8 is the NMR spectrum for fraction 6 of the distillation product asset forth above.

FIG. 9 is the infra-red spectrum for fraction 6 of the distillationproduct as set forth above.

The resulting product has a floral, green, galbanum-like fruity aroma.

EXAMPLE XVII PREPARATION OF p-METHYL PHENYLETHYL CYCLOHEXYL ETHER

Reaction: ##STR50##

246 grams of cyclohexene is added to a stirred slurry of p-methyl phenylbeta ethanol (408 grams) and 25 grams of Amberlyst® 15 cation exchangeresin maintained at 110° C., over a 2 hour period. The reaction mass isthen aged at 110° C. for an additional 3 hours whereupon it is cooledand filtered. The resulting solution is then heated at reflux with 80grams of 30% aqueous sodium hydroxide. The reaction mass is then cooledand the resulting organic layer is washed with 1 liter of water. Theorganic layer is separated from the reaction mass and distilled througha 11/2"×12" Goodlow packed column to afford the following distillationfractions:

    ______________________________________                                               Vapor    Liquid                  Weight                                Fraction                                                                             Temp.    Temp.    Pressure                                                                              Reflux of                                    Number (°C.)                                                                           (°C.)                                                                           mm/Hg.  Ratio  Fraction                              ______________________________________                                        1      50/56    104/106  .9 mm   4:1    15.7                                  2      65       124              4:1    32.6                                  3      65       126              4:1    18.8                                  4      95       128                     18.1                                  5      92       128      .8 mm           3.8                                  6      95       133      .75     9:1    12.9                                  7      95       137      .6      9:1    16.0                                  8      95       133      .6      1:1    31.4                                  9      95       133      .6      1:1    27.8                                  10     92       136      .5      1:1    22.9                                  11     92       136      .5      1:1    29.1                                  12     96       137      .5      1:1    30.4                                  13     94       143      .5      1:1    29.9                                  14     94       146      .5      1:1    28.5                                  15     94       151      .5      1:1    30.8                                  16     98       165      .5      1:1    30.0                                  17     95       180      .5      1:1    27.2                                  ______________________________________                                    

FIG. 10A is the GLC profile of the crude reaction product (conditions:1/8"×10' 10% SE 30 packed column programmed at 120°-220° C. at 16° C.per minute).

FIG. 10B is the GLC profile for fraction 8 of the foregoing distillation(conditions: 1/8"×10' 10% SE 30 packed column programmed at 220° C.isothermal).

FIG. 11 is the NMR spectrum for fraction 10 of the foregoingdistillation.

FIG. 12 is the infra-red spectrum for fraction 10 of the foregoingdistillation.

The resulting product having the structure: ##STR51## has an interestingintense, burnt fruit aroma.

EXAMPLE XVIII

Field tests are made each time using 100 male and 100 female Lasiodermaserricorne (F.) cigarette beetles. The beetles were released at acertain distance from the source of attraction which was treated withone of the cyclohexyl phenethylether derivatives prepared according toeither Example XVI or XVII. Further, felled trees having already beencontaminated with the respective beetles are positioned at both sides ofthe starting point. After a certain period of time the amount of insectsgathered at the source of attraction was determined thus indicating theeffectiveness of the pheromonal mixture according to the invention.

Field tests with Lasioderma serricorne (F.) are made whereby thedistance between the starting point and the source of attraction is 50meters. Four independent field tests were made whereby 42% of the malebeetles and 46% of the female beetles gathered at each catch tree. Theconcentration of insects at the catch tree was 55% of the male insectsand 58% of the female insects. In all these tests the catch tree wasimpregnated with a 0.7% ethanolic solution of one of the cyclohexylphenethylether derivatives of either Example XVI or XVII (7 grams ofcyclohexyl phenethylether derivative per 92 grams of 95% aqueousethanol).

EXAMPLE XIX

During two consecutive days several felled oak trees surrounding a fieldof tobacco plants were treated with 250 mg of one of the phenethylcyclohexylether derivatives of either Example XVI or XVII in 1.0%ethanolic solution. These trees were exposed in an area which werecontaminated with Lasioderma serricorne (F.). After 3 to 4 days 100beetles per square meter were observed on the logs. Other untreated logsor trees in the direct neighborhood of the treated logs or trees showedvery few (about 12) insects per square meter on the average while othertrees at a distance of 10 to 20 meters showed no contamination.

EXAMPLE XX

In a large test field, mixtures of one of the cyclohexyl phenethyletherderivatives of Example XVI or XVII in admixture with different DDTpreparation, fluorine-containing mixtures and arsenic-containingmixtures as well as hexachlorocyclohexane were used. These mixturescontained also small amounts of surface active agents and carriers. Themixtures were applied to catch trees namely logs of oak trees in an areaof tobacco plants contaminated with Lasioderma serricorne (F.). Thedistance between the catch trees was always 200 meters. After 8 daysthere was no contamination either in the tobacco fields or around theoak trees. About 92% of the Lasioderma serricorne (F.) insects weredestroyed. Surprisingly, is was found that after the fourth day theattracting effect was not diminished in spite of dead insects beingpresent. Furthermore, in those areas where one of the cyclohexylphenethylether derivatives of Example XVI or XVII was used alone, theaverage number of insects destroyed was about 80% which in itself issurprising. Thus, one of the cyclohexyl phenethylether derivatives ofExample XVI or XVII not only acts as a pheromone but also as aninsecticide. Furthermore, the entire area wherein one of the cyclohexylphenethylether derivatives of Example XVI or XVII was used had a faint,pleasant aroma (floral in the case of the cyclohexyl phenethyletherderivative of Example XVI and fruity in the case of the cyclohexylphenethylether derivative of Example XVII) covering any adverse andesthetically displeasing aroma of any other insecticides that were used.

EXAMPLE XXI

The following mixture is prepared:

    ______________________________________                                        Ingredient            Parts by Weight                                         ______________________________________                                        Phenylacetic acid     70.0                                                    Coumarin              20.0                                                    Phenylethylphenyl acetate                                                                           100.0                                                   Phenyl ethyl alcohol  5.0                                                     Benzyl benzoate       100.0                                                   Dimethylphenylethyl carbinol                                                                        10.0                                                    Methyl anthranilate   5.0                                                     Beta ionone           10.0                                                    Cyclohexyl hydrotropyl ether                                                  produced according to Example XVI                                                                   30.0                                                    ______________________________________                                    

The cyclohexyl hydrotropyl ether prepared according to Example XVIimparts the floral, green, galbanum-like and fruity aroma to this honeyfragrance while giving it a very warm undertone and imparting a verylong lasting floral top note to this fragrance.

EXAMPLE XXII PREPARATION OF A COSMETIC POWDER COMPOSITION

A cosmetic powder is prepared by mixing in a ball mill 100 grams oftalcum powder with 0.25 grams of the perfume composition preparedaccording to Example XXI. It has an excellent floral aroma.

EXAMPLE XXIII PERFUMED LIQUID DETERGENT

Concentrated liquid detergents (Lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818 issued onApr. 6, 1976) with floral aroma nuances and green, galbanum-like andfruity topnotes are prepared containing 0.10%, 0.15% and 0.20% of thefragrance prepared according to Example XXI. They are prepared by addingand homogeneously mixing the appropriate quantity of fragranceformulation prepared according to Example XXI in the liquid detergent.The detergents all possess excellent floral aromas with green,galbanum-like and fruity nuances, the intensity increasing with greaterconcentrations of perfume composition prepared according to Example XXI.

EXAMPLE XXIV PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

The composition prepared according to Example XXI is incorporated into acologne at concentrations of 2.0%, 2.5%, 3.0%, 4.0%, 4.5% and 5.0% in80%, 85%, 90% and 95% aqueous food grade ethanol and into handkerchiefperfumes at concentrations of 15%, 20% and 30% (in 80%, 85% and 95%aqueous food grade ethanol). A distinctive and definitive green,galbanum-like, fruity and full-bodied floral aroma is imparted to eachof the colognes and to each of the handkerchief perfumes at all levelsindicated.

EXAMPLE XXV PREPARATION OF SOAP COMPOSITION

100 grams of soap chips are mixed with 1 gram of the formulation ofExample XXI until a homogeneous composition is obtained. The homogeneouscomposition is heated under three atmospheres pressure at 180° C. for aperiod of three hours and the resulting liquid is placed into soapmolds. The resulting soap cakes, on cooling, manifest excellent floralaromas with green, galbanum-like and fruity nuances that are very longlasting.

EXAMPLE XXVI PREPARATION OF A SOLID DETERGENT COMPOSITION

A detergent is prepared from the following ingredients according toExample I of Canadian Pat. No. 1,007,948:

    ______________________________________                                                          Percent by Weight                                           ______________________________________                                        "Neodol 45-11" (a C.sub.14 -C.sub.15                                          alcohol ethoxylated with                                                      11 moles of ethylene oxide)                                                                       12                                                        Sodium carbonate    55                                                        Sodium citrate      20                                                        Sodium sulfate, water brighteners                                                                 q.s.                                                      ______________________________________                                    

This detergent is a "phosphate free" detergent. A total of 100 grams ofthis detergent is admixed with 0.15 grams of the honey based perfume ofExample XXI. Each of the detergent samples have an excellent floralhoney-like, green, galbanum-like and fruity aroma.

EXAMPLE XXVII DRYER-ADDED FABRIC SOFTENER ARTICLE

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396, a nonwoven cloth substrate useful as a dryer-added fabricsoftening article of manufacture is prepared wherein the substrate, thesubstrate coating and the outer coating and the perfuming material areas follows:

1. a water "dissolvable" paper ("Dissolvo Paper");

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. an outer coating having the following formulation (m.p. about 150°F.):

57% C₂₀₋₂₂ HAPS

22% isopropyl alcohol

20% antistatic agent

1% of cyclohexyl hydrotropyl ether prepared according to Example XVI

A fabric softening composition prepared as set forth above having agreen, galbanum-like and fruity and generally floral aromacharacteristic consists of a substrate having a weight of about 3 gramsper 100 square inches, a substrate coating of about 1.85 grams per 100square inches of substrate and an outer coating of about 1.4 grams per100 square inches of substrate, thereby providing a total aromatizedsubstrate and outer coating weight ratio of about 1:1 by weight of thesubstrate. A pleasant floral aroma is imparted in a pleasant manner tothe head space in the dryer on operation thereof using the saiddryer-added fabric softening nonwoven fabric.

EXAMPLE XXVIII

A liquid detergent composition prepared according to Example IV ofUnited Kingdom Pat. No. 1,498,520 whereby the following ingredients areadmixed:

    ______________________________________                                        Ingredient              Weight %                                              ______________________________________                                        Coconut alcohol ethoxylate                                                                            30%                                                   Linear alkyl benzene sulfonate,                                               triethanolamine salt (alkyl = C.sub.11.8 avg.)                                                        8%                                                    Potassium chloride      3%                                                    Triethanolamine         3%                                                    Triethanolammonium citrate                                                                            2%                                                    Ethyl alcohol           5%                                                    Soil release ether "D"  1.0%                                                  Cyclohexyl hydrotropyl ether prepared                                         according to Example XVI                                                                              5.0%                                                  Water                   Balance                                               ______________________________________                                    

The soil release ether "D" is defined according to Table II on page 15of United Kingdom Pat. No. 1,498,520.

This composition is prepared by admixing all of the ingredientsexclusive of soil release ether "D" and agitating the mixture until allelectrolytes are dissolved. Soil release ether "D" is then admixed withthe solution in the form of a dry powder which passes through a 150 meshstandard sieve. The resulting composition is in the liquid state and iseasily pourable. The composition is found not to redden on contact withplastic bottles, does not gel when diluted with water and has along-lasting aroma which can be described as green, galbanum-like,fruity and rich floral and rather long lasting. Indeed, the aroma lastsfor several weeks when exposed to the atmosphere.

This composition is added to an aqueous laundrying bath at aconcentration of 0.20% (weight) at a temperature of 55° C., waterhardness 7 grains per gallon and a pH of 10.0. Polyester and mixedpolyester/cotton fabrics are laundered in the bath for a period of 10minutes after which the fabrics are thoroughly rinsed with fresh waterand dried at ambient temperatures. The fabrics are provided with a soilrelease finish. The head space above the fabrics has a pleasant faintaroma which can be described as floral, green, galbanum-like and fruityand also rather long lasting (about 3 days).

EXAMPLE XXIX PREPARATION OF A COSMETIC POWDER COMPOSITION

A cosmetic powder is prepared by admixing in a ball mill, 100 grams oftalcum powder with 0.25 grams of cyclohexyl hydrotropyl ether preparedaccording to Example XVI. The resulting cosmetic powder has an excellentgreen, floral, galbanum-like and fruity aroma which is very longlasting.

EXAMPLE XXX PERFUMED LIQUID DETERGENT

Concentrated liquid detergents (Lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818 issued onApr. 6, 1976) with floral, green, galbanum-like and fruity aroma areprepared containing 0.10%, 0.15%, 0.20% and 0.25% of cyclohexylhydrotropyl ether prepared according to Example XVI. They are preparedby adding and homogeneously admixing the appropriate quantity ofcyclohexyl hydrotropyl ether in the liquid detergent. The detergents allpossess intense, long-lasting floral, green, galbanum-like and fruityaroma characteristics.

EXAMPLE XXXI PREPARATION OF COLOGNES AND HANDKERCHIEF PERFUMES

Cyclohexyl hydrotropyl ether prepared according to Example XVI isincorporated into colognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%,4.0% and 4.5% in 80%, 85%, 90% and 95% aqueous food grade ethanol; andinto handkerchief perfumes at concentrations of 15%, 20%, 25% and 30%(in 80%, 90% and 95% aqueous ethanol). Distinctive floral, green,galbanum-like and fruity aroma nuances which are very long lasting ondry-out (46 hours) are imparted to the colognes and to the handkerchiefperfumes at the various levels indicated above.

What is claimed is:
 1. The cyclohexyl phenethylether derivative whereinthe structure of the cyclohexyl phenethylether is: ##STR52##